Photographic silver halide emulsion

ABSTRACT

A photographic silver halide emulsion containing at least one sensitizing dye represented by the general formula I   wherein Z1 represents a nonmetallic atomic group forming a 4quinoline nucleus, Z2 represents a nonmetallic atomic group necessary to complete a member selected from the group consisting of a 5-membered heterocyclic ring and a 6-membered heterocyclic ring, R1 and R2 each represents a member selected from the group consisting of a nonsubstituted alkyl group and a substituted alkyl group, R3 represents a member selected from the group consisting of a hydrogen atom and an alkylene group condensed with R2, X represents an acid anionic group, and p and m each represents 1 or 2, said X forming an intramolecular salt when p is 1, and AT LEAST ONE COMPOUND REPRESENTED BY THE GENERAL   WHEREIN D represents a divalent aromatic residual group, R4 and R6 each represents a member selected from the group consisting of a hydrogen atom, a hydroxyl group, a halogen atom, an alkoxyl group, an aryloxyl group, and arylthio group, R5 represents a member selected from the group consisting of an aryloxyl group and an arylthio group, and W represents a member selected from the group consisting of CH and N.

United States Patent [72] Inventors Kelsuke Shiba;

Masanao l-linata; Hiroshl Misu; Masao Sawahara, all of Kanagawa, Japan [21] Appl. No. 707,478

[22] Filed Feb. 23, 1968 [45] Patented Nov. 2, 1971 [73] Assignee Fuji Photo Film Co., Ltd.

Kanagawa, Japan [32] Priority Feb. 23, 1967 [3 3] Japan [3 l 42/1 1669 [54] PHOTOGRAPHIC SILVER HALIDE EMULSION 8 Claims, No Drawings [52] U.S. Cl 96/126, 96/109 [51] Int. Cl. G03c 1/28 [50] Field of Search ..96/104, 109

[56] References Cited UNITED STATES PATENTS 2,945,762 7/1960 Carroll et al 96/104 3,416,927 12/1968 Kalenda 96/104 Primary Examiner-J. Travis Brown Attorney-Sughrue, Rothwe ll Mion, Zinn & Macpeak ABSTRACT: A photographic silver halide emulsion containing at least one sensitizing dye represented by the general formula I wherein Z represents a nonmetallic atomic group forming a 4-quinoline nucleus, 2 represents a nonmetallic atomic group necessary to complete a member selected from the group consisting of a S-membered heterocyclic ring and a 6-membered heterocyclic ring, R and R each represents a member selected from the group consisting of a nonsubstituted alkyl group and a substituted alkyl group, R represents a member selected from the group consisting of a hydrogen atom and an alkylene group condensed with R X represents an acid anionic group, and p and m each represents 1 or 2, said X forming an intramolecular salt when p is l and at least one compound represented by the general W N N wherein D represents a divalent aromatic residual group, R

and R each represents a member selected from the group consisting of a hydrogen atom, a hydroxyl group, a halogen atom, an alkoxyl group, an aryloxyl group, and arylthio group, R represents a member selected from the group consisting of an aryloxyl group and an arylthio group, and W represents a member selected from the group consisting ofCH and N.

PHOTOGRAPHIC SILVER HALIDE EMULSION BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a spectral sensitized photographic silver halide emulsion and in particular to a photographic silver halide emulsion in which the formation of photographic fogs caused by the addition of a sensitizing dye is inhibited and the reduction of the color sensitivity during the preservation is prevented.

2. Description of the Prior Art It is well known to spectrally sensitize a photographic silver halide emulsion by incorporating a sensitizing dye in the photographic silver halide emulsion, whereby the range of light-sensitive wavelength is further enlarged ,to a longer wavelength side. The strength of the spectral sensitization is influenced by the chemical structure of the sensitizing dye to be employed, the properties of the emulsion, such as, the composition of silver halide, the crystal structure of the silver halide, the concentration of silver ion, the pH of the emulsion and the like, as well as the kinds of additives, such as stabilizer, wetting agent, hardening agent and a coupler. Many of the aforesaid additives to be incorporated in a photographic silver halide emulsion together with a sensitizing dye act to weaken the spectral sensitization of the sensitizing dye.

Moreover, although by the addition of a sensitizing dye to a silver halide emulsion, the silver halide emulsion is spectrally sensitized, it usually has a bad influence on the photographic properties of the photographic silver halide emulsion. In particular, the formation of fog caused by the addition of a sensitizing dye (hereinafter, such a fog is called dye fog) and the instability of the dye sensitivity greatly hinders the preparation of a photographic light-sensitive element having high strength spectral sensitivity, reduced fog and good preservability. When a sensitizing dye is used together with a conventionally employed antifoggant or a stabilizer for improving these drawbacks, the spectral sensitivity is remarkably reduced in some cases. Further, the spectral sensitivity is degraded extremely in other cases when the material is stored. Thus, forobtaining effective results, the aforesaid additives must be selected strictly in accordance with the sensitizing dye to be employed.

An object of the present invention is to provide a photographic silver halide emulsion sensitized by a spectral sensitizing method, in which the formation of dye fogs is inhibited and the degradation of spectral sensitivity with the lapse of time is reduced without lowering the spectral sensitivity.

Another object of the present invention is to provide an excellent red-sensitive silver halide emulsion for color photographic light sensitive materials.

SUMMARY OF THE INVENTION According to the present invention, there is provided a photographic silver halide emulsion containing a sensitizing dye represented by the general formula I "Z1 R3 R I I-CH=CH-C J=CHCH=( J=(CHCH=)m-ri$m (X na wherein Z represents a nonmetallic atomic group necessary to complete a 4-quinoline nucleus, Z represents a nonmetallic atomic group necessary to complete a S-membered or 6-membered heterocyclic ring, R, and R each represent an unsubstituted or substituted alkyl group, R represents a hydrogen atom or an alkylene group condensed with said group R X represents an acid anion, and p and m each represent 1 or 2, said X forming an intramolecular salt when p is l, and a compound represented by the general formula (II):

wherein D represents a divalent aromatic residual group, R and R each represent a hydrogen atom, a hydroxyl group, a halogen atom, an alkoxyl group, an aryloxyl group, or an arylthio group, R and R each represent an aryloxyl group or an arylthio group, and W represents CH or N.

In General formula I, the 4-quinoline nucleus shown by Z, may have a substituent such as a halogen atom, an alkyl group, or an alkoxyl group. The examples of the heterocyclic rings to be completed by the nonmetallic atomic group represented by Z are a 4-quinoline nucleus, a 2-quinoline nucleus, a naphthothiazole nucleus, an oxazole nucleus, and a benzimidazole nucleus. Also, R or R may be a lower alkyl group such as a methyl group, an ethyl group or a propyl group or a substituted group thereof such as a B-hydroxyethyl group, ,B-acetoxyethyl group, or ethylsulfate group; a carboxyalkyl group or a derivative thereof such as a carboxymethyl group or a 2-(2-carboxy-ethoxy) ethyl group; a sulfoalkyl group or a derivative thereof such as a B-sulfoethyl group, a B- sulfopropyl group, or a 3-methoxy-2-(3-sulfopropoxy) propyl group. The main feature of the sensitizing dye having the chemical structure shown by general formula I is that it contains at least one quinoline heterocyclic nucleus.

In general formula II, the examples of the divalent aromatic residual group represented by D are a biphenylene group, a naphthalene group, a stilbene group and a bibenzyl group.

The main feature of the compound represented by general formula II is that each of the pyrimidinylamino nuclei or triazinylamino nuclei bonded by the divalent aromatic residual group has at least one arylthio group or aryl oxyl group.

The sensitizing dye represented by general formula I (hereinafter the sensitizing dye is called Sensitizing Dye I) can spectrally sensitize a photographic silver halide emulsion in a wavelength region of from a green region to a red region by properly selecting the heterocyclic nucleus shown by However, there is a fault that in the case of incorporating in a silver halide emulsion the sensitizing dye alone, dye fogs tend to be formed and also the color sensitivity by the sensitizing dye is lowered in course of time.

The compound shown by general formula II (hereinafter it is called compound II) does not substantially have spectral absorption at visible ranges but has a strong absorption at a near ultraviolet region. When sensitizing dye I is incorporated in a silver halide emulsion together with compound II for sensitizing the silver halide emulsion, the formation of dye fogs can be effectively inhibited and markedly prevented without substantially reducing the spectral sensitivity. Compound ll of this invention provides the aforesaid merits or effects selectively to only the carbocyanine sensitizing dye represented by general formula I, that is, a sensitizing dye showing a M-band type spectral sensitization among various carbocyanine dyes and when compound II is incorporated in a photographic silver halide emulsion together with other carbocyanine dyes showing a J-band type or H-band type spectral sensitization, the spectral sensitivity is markedly reduced on the contrary.

Moreover, among the compounds II used in this invention, the one of which the pyrimidinylamino nuclei each having at least one aryl oxyl group or arylthio group has such merits when used together with sensitizing dye I in a photographic silver halide emulsion for color photographic light-sensitive 1 materials that the contamination by color development is prevented, the formation of stains by the sensitizing dye is reduced and the reduction of spectral sensitization by the presence of a coupler is prevented besides the aforesaid spectral sensitivity, and the prevention of the reduction in color sensitivity in course of time.

The practical examples of the sensitizing dyes represented by general formula I are shown below although the sensitizing dye is not limited to them only:

Also, the typical examples of the compound represented by General formula II are as follows:

I Cl

SO Nu SO Na SO Na.

| S0 Na N 0- -NH- -cm 4121140000113 I 5 N SO;Na

i somu "1' Among the compounds represented by General formula II,

the compound in which Z is -N-, that is, the compound having 60 a S-triazine nucleus may be prepared by a well-known method. The compound in which Z is -CH-, that is, having a pyrimidine nucleus may be prepared as follows:

Preparation of Compound IIb In 70 ml. of dimethylformamide were heated under refluxing for about 2.5 hours 14.1 g. of Compound Ilg prepared above; 13.3 g. sodium-B-naphtholate, and 1.0 g. of 1,4-diaza- 2,2, 2-bicyclooctane.

After allowing to cool, the precipitates formed were removed by filtering and the filtrate was subjected to distillation under reduced pressure to remove dimethylformamide. The residue was dissolved in methanol and mixed with about 5 ml. of concentrated hydrochloric acid to deposit a crystal of the objective compound, which was collected by filtering, washed with a small amount of acetone and water, and then dried.

PREPARATION 3 Preparation of Compound Ilf In a mixed solvent of 70 ml. of water and 20 ml. of dioxane were heated under refluxing 14.1 g. of compound llg, 1.0 g. of sodium hydroxide and 4.4 g. of thiophenol. After the reaction was finished, about 5 ml. of concentrated hydrochloric acid was added to the reaction mixture to precipitate the product, which was collected by filtering, washed with water and methanol, and dried.

Sensitizing dye l or compound II in this invention may be incorporated in a silver halide emulsion as an aqueous solution t rsqtlq a o i mlhsrwfia5232969 Olvem Such as methanol, ethanol, alkaline methanol, and the l ike separately, or as a mixture thereof. The amounts thereof and the ratio thereof are suitably selected in accordance with the kinds of each compound, the emulsion to be employed and additives.

A suitable concentration of sensitizing dye I, however, is 0.002-0.2 g. per 1 g. molecule of the silver halide in a silver halide emulsion and a suitable concentration of compound 11 is 0.01- g. per 1 g. molecule of the silver halide in a silver halide emulsion, and a preferable concentration ratio of Senby a conventional manner and may be applied to a suitable support such as a cellulose derivative film or a baryta coated paper.

Now the invention will further be described by referring to the following practical examples.

EXAMPLE 1 A definite amount of a 4X10" mol methanol solution of Sensitizing dye l in this invention was added to 100 g. (AgX: 33x10 mol) of silver chloro-bromide emulsion prepared by a conventional method and a definite amount of a 0.1 percent methanol solution of compound II was immediately added to the resulting emulsion. The mixture was stirred for 1 hour at 40 C. and applied to a support in a thickness of 7 ml. per cabinet size followed by drying.

The light sensitive element thus prepared was exposed by using an optical wedge through a blue filter transmitting only light having shorter wavelengths than 500 m. p. and a yellow filter transmitting only light having longer wavelengths than 500 m. p. and then developed for 10 minutes at 20 C. in a developer having the composition shown below, followed by fixing.

Metol 0.3 3. Potassium Pyrosulfite 1.4 g Sodium Sulfite (anhydrous) 38 g. Hydroquinone 6 g. Sodium Carbonate (Monohydrate) 22.5 g. Potassium Bromide 0.9 g. Citric Acid 0.7 g. Water To Make I00 ml.

For the thus developed light sensitive element, the density, the blue sensitivity (S using a blue filter, and the spectral sensitivity (S using a yellow filter were measured, the results of which are shown in table 1.

Filter relative Sensi- Comsensitivity Experiment tizing Amt. pound Amt. Number dye (mL) II (mL) SB Sm Fog TABLE 1 Filter relative Sensi- Comsensitivity Experiment tizing Amt. ound Amt. Number dye (mL) I (mL) Sn Sm Fog 1. 0 100 100 0. 12 2. 0 100 141 0. 15 1-.. IA 4.0 Ila, 71 141 0.21 2. 0 4 117 200 0. 10 2. 0 b 200 0. 08

. 2. 0 i 4 117 200 0. 08 IA 2. 0 l t s 117 200 0.07

1. 0 05 170 0. 85 w 2. 0 71 200 0. 7 4 2.0 4 117 282 0. 01s 2. 0 h 310 0. 05

l 1.0 110 214 0.08 2. (l 1" 1...5 0 Oil 5 s 2.0 4 12:1 320 0.01; l 2. 1) h 125 320 l). 07

1. 0 100 0.10 2. 0 100 170 0. 30 (L [E 4. 0 I 10 1 70 200 0. 44 l 2. 0 1 4 100 220 0. 24 2. 0 8 100 235 0. 22

l .2. 0 l 4 110 340 0. 16 7 2.0 i 1 x 110 340 0.10

From the above results, it will be understood that by incorporating in a photographic light sensitive emulsion Sensitizing dye l and compound II simultaneously, the color sensitivity of the emulsion is increased and the formation of fogs is inhibited.

EXAMPLE 2 A definite amount of a 4X10 mol methanol solution of Sensitizing dye l and a definite amount of a 0.1 percent methanol solution of compound 11 were added to 100 g. (AgX: 3O 10 mol) of a silver bromide emulsion prepared by a conventional method. The resulting emulsion was stirred for 30 minutes at 40 C., mixed with a hardening agent and a wetting agent, and applied to a film base followed by drying.

The light sensitive film was stored at a temperature of 24-30 C. and a relative humidity of 65 -70 percent and the spectral sensitivity (S using a yellow filter was measured as in example 1 the results ofwhich are shown in table 2.

TAB LE 2 Filter relative sensitivity, Sspc Direetly after coating Sensi- Comtizlng Amt. pound dye (ml.) II

Experiment No.

After 1 After 4 month month Amt. (1111.)

i l l We claim:

wherein Z represents a nonmetallic atomic group forming a nucleus of the 4-quinoline series, Z represents a nonmetallic atomic group necessary to complete a member selected from the group consisting of a 4-quinoline nucleus, a 2-quinoline nucleus, a naphthothiazole nucleus, an oxazole nucleus, and a benzimidazole nucleus, R, and R each represents a member selected from the group consisting of an alkyl group, a hydroxyalkyl group, an acetoxyalkyl group, an alkylsulfate group, a carboxyalkyl group, a carboalkoxyalkyl group, a sulfoalkyl group, an alkoxysulfoalkoxyalkyl group, R represents a member selected from the group consisting of a hydrogen atom and an alkylene group having 2-5 carbon atoms capable of condensing with R X represents an acid anionic group,, and P and m each represents 1 or 2, said X forming an intramolecular salt when P is l, and at least one compound represented by the following general formula:

wherein D represents a divalent aromatic residual group selected from the group consisting of a biphenylene group a phenylene group a naphthylene group (-C l-l ),a stilbene group and a bibenzyl group R. and R each represents a member selected from the group consisting of a hydrogen atom, a hydroxyl group, a halogen atom, an alkoxyl group, an aryloxyl group and arylthio group,

R and R, each represents a member selected from the group consisting of an aryloxyl group and an arylthio group, and W represents a member selected from the group consisting of CH and N.

2. The photographic silver halide emulsion as claimed in claim 1 wherein said sensitizing dye is a compound selected from the group consisting of:

I Q A 3. The photographic silver halide emulsion as claimed in claim 1 wherein said compound represented by general formula II is selected from the group consisting of:

/N\ NHU o N soaNa rfi I I and 4. The emulsion of claim 1 wherein said D is substituted with an -SO M group, where M is selected from the group consisting of a hydrogen atom and a metal which forms a water-soluble salt.

5. The emulsion of claim 1 wherein said silver halide is selected from the group consisting of silver iodobromide, silver bromide, silver chlorobromide and silver chloride.

6. The photographic silver halide emulsion as claimed in claim 1, wherein the concentration of said sensitizing dye is 0.002-0.2 g. per gram molecule ofthe silver halide.

7. The photographic silver halide emulsion as claimed in claim 1, wherein the concentration of said compound represented by the general formula II is 0.02-10 g. per gram molecule of the silver halide.

8. The photographic silver halide emulsion as claimed in claim 1, wherein the concentration ratio of said sensitizing dye of formula I to said compound represented by the general formula II is from I :2 to 1:200.

* t k k 

2. The photographic silver halide emulsion as claimed in claim 1 wherein said sensitizing dye is a compound selected from the group consisting of:
 3. The photographic silver halide emulsion as claimed in claim 1 wherein said compound represented by general formula II is selected from the group consisting of:
 4. The emulsion of claim 1 wherein said D is substituted with an -SO3M group, where M is selected from the group consisting of a hydrogen atom and a metal which forms a water-soluble salt.
 5. The emulsion of claim 1 wherein said silver halide is selected from the group consisting of silver iodobromide, silver bromide, silver chlorobromide and silver chloride.
 6. The photographic silver halide emulsion as claimed in claim 1, wherein the concentration of said sensitizing dye is 0.002-0.2 g. per gram molecule of the silver halide.
 7. The photographic silver halide emulsion as claimed in claim 1, wherein the concentration of said compound represented by the general formula II is 0.02- 10 g. per gram molecule of the silver halide.
 8. The photographic silver halide emulsion as claimed in claim 1, wherein the concentration ratio of said sensitizing dye of formula I to said compound represented by the general formula II is from 1:2 to 1:200. 